WO2010118022A2 - System and method for conditioning biomass-derived synthesis gas - Google Patents
System and method for conditioning biomass-derived synthesis gas Download PDFInfo
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- WO2010118022A2 WO2010118022A2 PCT/US2010/030090 US2010030090W WO2010118022A2 WO 2010118022 A2 WO2010118022 A2 WO 2010118022A2 US 2010030090 W US2010030090 W US 2010030090W WO 2010118022 A2 WO2010118022 A2 WO 2010118022A2
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0259—Physical processing only by adsorption on solids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0872—Methods of cooling
- C01B2203/0888—Methods of cooling by evaporation of a fluid
- C01B2203/0894—Generation of steam
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
- C10J2300/0909—Drying
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0959—Oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1618—Modification of synthesis gas composition, e.g. to meet some criteria
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1861—Heat exchange between at least two process streams
- C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/145—Feedstock the feedstock being materials of biological origin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- the present invention relates to a method of conditioning biomass-derived synthesis gas. More specifically, the method is suitable for providing conditioned synthesis gas suitable for production of Fisher-Tropsch fuel. Still more specifically, the method comprises conditioning biomass-derived synthesis gas via thermal conversion with enriched oxygen.
- a major drawback with biomass gasification and/or pyrolysis technology is that the hydrogen (H 2 ) to carbon monoxide (CO) ratio is generally too low while the content of methane and higher hydrocarbons as well as the carbon dioxide content are undesirably high for downstream processes such as Fisher-Tropsch (FT) synthesis.
- FT Fisher-Tropsch
- the WGS also fails to reform undesired methane (and higher hydrocarbons) into H 2 and CO for use as a feedstock in a Fischer-Tropsch process.
- the un- reacted methane instead acts as an inert for the Fischer-Tropsch process, lowering carbon utilization and conversion to Fischer-Tropsch fuels.
- a system and process for conditioning synthesis gas e.g., biomass-derived synthesis gas
- thermal conversion process comprising: providing a first synthesis gas having a first H 2 :CO ratio of less than a minimum value or greater than a maximum value; providing enriched oxygen; and subjecting the first synthesis gas to partial oxidation in the presence of at least a portion of the enriched oxygen to produce a conditioned synthesis gas having a desired ratio of H 2 :CO in the range of from the minimum value to the maximum value.
- the minimum value is about 0.7 and the maximum value is about 2.0.
- the minimum value is about 0.7 and the maximum value is about 1.5.
- the minimum value is about 0.75 and the maximum value is about 1.1.
- the partial oxidation reaction is carried out in a reactor.
- the thermal conversion process is a non-catalytic, high temperature process.
- the high temperature may be a temperature in the range of from about 950 0 C to about 1500 0 C.
- the high temperature may be a temperature in the range of from about 950 0 C to about 1400 0 C.
- the process may further comprise adjusting the portion of enriched oxygen based on a desired H 2 : CO ratio.
- providing enriched oxygen comprises providing enriched oxygen at a flow rate in the range of from about 10 lb/h per ton of dry biomass feed to about 100 lb/h per ton of dry biomass feed.
- providing enriched oxygen comprises Vacuum Swing Adsorption (VSA).
- VSA Vacuum Swing Adsorption
- the enriched oxygen can comprise from about 50 vol% to about 100 vol% oxygen, alternatively from about 50 vol% to about 95 vol% oxygen.
- the enriched oxygen can further comprise nitrogen and trace gases present in air.
- providing the first synthesis gas comprises pyrolizing or gasifying a carbonaceous feedstock.
- the method can further comprise adjusting the moisture content of the first synthesis gas by adjusting the moisture content of the carbonaceous feedstock.
- the first synthesis gas is obtained via gasification.
- the carbonaceous feedstock comprises biomass.
- the conditioned synthesis gas is suitable for FT liquids production.
- the conditioned synthesis gas has a H 2 ICO ratio on the range of from about 0.75 to about 1.1.
- the conditioned synthesis gas has a H 2 : CO ratio on the range of from about 1.5 to about 2.0.
- the first synthesis gas has a H 2 :CO ratio in the range of from 0.3 to 1.0 on a dry basis.
- Also disclosed herein is a method of producing FT product liquids, the method comprising: (a) providing a conditioned synthesis gas according to the disclosed process; and (b) producing FT product liquids by subjecting the conditioned synthesis gas to FT reaction under FT operating conditions.
- the method further comprises cooling the conditioned synthesis gas via production of high pressure steam, low pressure steam, or a combination thereof.
- the tar content in the conditioned synthesis gas is less than 10% of the tar content in the first syngas.
- the method further comprises compressing the cooled conditioned synthesis gas prior to (b).
- a system for conditioning synthesis gas for production of liquid hydrocarbons via FT synthesis comprising: enriched oxygen production apparatus configured to provide enriched oxygen from air; and a synthesis gas conditioning reactor fluidly coupled with the enriched oxygen production apparatus, wherein the synthesis gas conditioning reactor is configured for subjecting a first synthesis gas having a first H 2 : CO ratio outside a desired range to partial oxidation in the presence of at least a portion of the enriched oxygen to produce a conditioned synthesis gas having a second H 2 : CO within the desired range.
- the desired range is from about 0.75 to about 2.
- the enriched oxygen production apparatus can comprise vacuum swing adsorption.
- the enriched oxygen comprises from about 50vol% to about 100vol% oxygen.
- the synthesis gas conditioning reactor is operable in the absence of catalyst. In embodiments, the synthesis gas conditioning reactor is operable at a temperature in the range of from about 950 0 C to about 1500 0 C.
- the system may further comprise synthesis gas production apparatus configured for the production of the first synthesis gas from a carbonaceous material.
- the synthesis gas production apparatus may comprise a gasifier.
- the carbonaceous material comprises biomass.
- the system further comprises at least one FT reactor downstream of the synthesis gas conditioning reactor and configured for the production of FT hydrocarbons from the conditioned synthesis gas.
- the at least one FT reactor comprises
- the FT catalyst can be iron-based.
- the system can further comprise at least one heat exchange device configured for the production of high pressure steam or low pressure steam via heat transfer from the conditioned synthesis gas.
- Figure 1 is a flow diagram of a system for conditioning synthesis gas according to an embodiment of this disclosure. NOTATION AND NOMENCLATURE
- ratio' for example, the ratio of hydrogen to carbon monoxide in synthesis gas
- a system and method for conditioning synthesis gas for use in a Fischer-Tropsch process utilizes a non-catalytic high temperature thermal conversion process using an enriched oxygen source for the conversion of methane and higher hydrocarbons in a biomass-derived synthesis gas from a gasification and or pyrolysis process into H 2 and CO, thus providing an optimal H 2 /CO ratio, suitable for use in downstream processes, for example, downstream FT synthesis.
- the H 2 /CO ratio of biomass-derived synthesis gas is adjusted (e.g., increased) via partial oxidation of the biomass-derived synthesis gas with an enriched oxygen/nitrogen stream and reforming of methane into H 2 and CO.
- a system for carrying out the method comprising a thermal conversion reactor (also referred to herein as a syngas conditioning reactor).
- the reactor is configured to convert methane and higher hydrocarbons from a biomass-derived syngas into H 2 and CO, in the absence of catalyst.
- the system is configured to provide a desired H 2 /CO ratio, suitable for use in a downstream FT synthesis process.
- the system and method utilize an enriched oxygen stream (e.g., with an oxygen content in the range of 50-100 vol%, or 50-95vol% with the remaining comprising of nitrogen and/or other trace gases in the inlet air) to perform thermal conversion of a syngas stream (e.g., a biomass-derived synthesis gas) in the absence of a catalyst.
- a syngas stream e.g., a biomass-derived synthesis gas
- the H 2 /CO ratio of the feed synthesis gas may be adjusted (e.g., optimized) for use in FT processes.
- FIG. 1 is a flow diagram of a system I according to an embodiment of this disclosure.
- System I comprises enriched oxygen production apparatus 100 and synthesis gas conditioning reactor 200.
- enriched oxygen production apparatus 100 may be any apparatus suitable for producing high purity oxygen from air, description will be made wherein enriched oxygen production apparatus 100 comprises vacuum swing adsorption (VSA) apparatus.
- System I may further comprise syngas production apparatus 10, synthesis gas compression apparatus 300, one or more additional synthesis gas cleanup units as indicated as 400, one or more Fischer-Tropsch reactors 500, or a combination thereof.
- VSA apparatus 100 is configured to provide an enriched oxygen stream 113 from inlet air 101.
- VSA apparatus 100 may be any VSA apparatus known in the art to provide enriched oxygen from inlet air.
- VSA apparatus 100 comprises at least one adsorption vessel 108 (two indicated in Figure 1).
- VSA apparatus 100 may further comprise inlet filter 102, air blower 103, vacuum blower 105, discharge silencer 106, vent line 107, oxygen gas or GOX cooler 110, GOX buffer vessel 111, GOX compressor 112, or some combination thereof. These unit components may be connected as indicated in Figure 1.
- Vacuum Swing Adsorption (VSA) apparatus 100 provides an enriched oxygen stream.
- the enriched oxygen stream may comprise from about 50% to about 100% O 2 by volume, alternatively, from about 50% to about 95% O 2 by volume.
- the enriched oxygen may further comprise nitrogen and trace gases present in air.
- System I further comprises synthesis gas conditioning reactor 200.
- Synthesis gas conditioning reactor 200 is coupled with VSA apparatus 100.
- outlet line 113 carrying enriched oxygen from VSA adsorption is connected with an inlet of synthesis gas conditioning reactor 200 via GOX preheater 114 and line 117.
- Synthesis gas conditioning reactor 200 is configured for subjecting a first synthesis gas to partial oxidation in the presence of at least a portion of the enriched oxygen produced in VSA apparatus 100 to produce a conditioned synthesis gas having a desired ratio of H 2 : CO.
- An inlet line 118 may introduce the first synthesis gas into the syngas conditioning reactor 200.
- Inlet line 118 may be connected with a synthesis gas production apparatus 10, as discussed further hereinbelow.
- Synthesis gas conditioning reactor 200 can comprise one or more burners 212 at which partial synthesis gas to be conditioned and enriched oxygen are intimately contacted.
- synthesis gas conditioning reactor 200 comprises a plurality of burners distributed along the top of reactor 200.
- synthesis gas conditioning reactor 200 comprises at least one burner having a diameter of at least 2 inches, at least three inches or at least four inches.
- synthesis gas conditioning reactor 200 comprises at least 2, at least 5, at least 10, at least 20, at least 50, or at least 100 burners.
- the burners may be positioned in any suitable arrangement within reactor 200.
- burner(s) 112 are circumferentially distributed at the top of reactor 200. In embodiments, burner(s) 112 are distributed uniformly about a cross-section of reactor 200.
- the first synthesis gas may have a first H 2 :CO ratio of less than a minimum value or greater than a maximum value, and syngas conditioning reactor 200 is operable to provide a conditioned synthesis gas having a desired H 2 ICO ratio in the range between the minimum value and the maximum value.
- the first synthesis gas may be a product of pyrolizing or gasifying a carbonaceous feedstock to produce the first synthesis gas.
- the carbonaceous feedstock is biomass.
- System I may further comprise synthesis gas production apparatus 10.
- Synthesis gas production apparatus is configured for producing the first synthesis gas from a carbonaceous feedstock introduced thereto via carbonaceous material inlet line 5.
- synthesis gas production apparatus 10 comprises a gasifier.
- System I may further comprise a GOX preheater 114 configured for heating the GOX prior to introduction into synthesis gas conditioning reactor 200. Steam may be introduced into GOX preheater 114 and condensate produced via heat transfer to the enriched oxygen in line 113 removed from GOX preheater 114 via condensate line 116. Preheated enriched oxygen may be introduced into syngas conditioning reactor 200 via line 117. [0035] System I may further comprise one or more heat transfer devices configured for removal of heat from the conditioned synthesis gas produced in synthesis gas conditioning unit 200.
- boiler 203, high pressure (HP) steam boiler/superheater 202, and low pressure (LP) steam boiler 209 are configured for production of steam from boiler feed water via heat transfer with conditioned synthesis gas exiting synthesis gas conditioning reactor 200 via outlet line 201.
- System I may further comprise synthesis gas compression apparatus 300.
- Synthesis gas compression apparatus 300 is positioned downstream of synthesis gas conditioning apparatus 200 and may be positioned downstream of one or more heat transfer devices (e.g., boiler 203, HP steam boiler/superheater 202, and/or LP steam boiler 209).
- Synthesis gas compression apparatus 300 comprises one or more compressor configured for compressing conditioned synthesis gas or cooled/conditioned synthesis gas.
- synthesis gas compression apparatus 300 comprises four compressors, 301a, 301b, 301c, and 30 Id.
- System I may further comprise additional syngas cleanup units 400.
- Such units may be configured for removing one or more undesirable components from the conditioned synthesis gas prior to downstream FT synthesis.
- Additional syngas cleanup units 400 may be downstream of syngas compression apparatus 300, downstream of one ore more heat removal units (e.g., boiler 203, HP steam boiler/superheater 202, and/or LP steam boiler 209), or both.
- Additional syngas cleanup units 400 may comprise, for example, one or more AGR units.
- a line 303 may be configured to introduce compressed conditioned synthesis gas into additional synthesis gas cleanup unit(s) 400.
- System I may further comprise one or more FT reactor 500.
- FT reactor 500 is any reactor known in the art to be suitable for the production of liquid hydrocarbons from synthesis gas.
- FT reactor 500 contains therein a bed of FT catalyst.
- the FT catalyst may be supported or unsupported.
- the FT catalyst is a precipitated, supported catalyst.
- the FT catalyst is a precipitated, unsupported catalyst.
- the catalyst is an iron-based FT catalyst.
- the iron-based catalyst is promoted with potassium and/or copper.
- a line 401 may be configured to introduce conditioned synthesis gas into FT reactor 500.
- One or more outlet lines 501 may be coupled with FT reactor 500 for removal of FT products therefrom.
- the method comprises: providing a first synthesis gas having a first H 2 ICO ratio of less than a minimum value or greater than a maximum value; providing enriched oxygen; and subjecting the first synthesis gas to partial oxidation in the presence of at least a portion of the enriched oxygen to produce a conditioned synthesis gas having a desired ratio of H 2 ICO in the range of from the minimum value to the maximum value.
- Providing Synthesis Gas to be Conditioned The disclosed method comprises providing a synthesis gas to be conditioned, the synthesis gas to be conditioned having a first H 2 :CO ratio of less than a minimum value or greater than a maximum value.
- the synthesis gas to be conditioned in syngas conditioning reactor 200 may be the product of pyrolysis and/or gasification of a carbonaceous feedstock.
- the carbonaceous feedstock comprises biomass.
- providing syngas to be conditioned comprises introducing carbonaceous feedstock into syngas production unit(s) 10 via carbonaceous feedstock inlet line 5, and operating the syngas production unit(s) such that the feedstock is converted to synthesis gas to be conditioned.
- the synthesis gas to be conditioned may be obtained via gasification.
- the synthesis gas to be conditioned in syngas conditioning reactor 200 may have a first H 2 :CO ratio of less than a minimum value or greater than a maximum value. In applications, the minimum value is about 0.7 and the maximum value is about 2.0.
- the minimum value is about 0.7 and the maximum value is about 1.5. In applications, the minimum value is about 0.75 and the maximum value is about 1.1.
- the moisture content of the synthesis gas to be conditioned is controlled by reducing the moisture content of the feed (e.g. of the biomass) introduced into the synthesis gas production unit(s). For example, the moisture content of biomass fed to a gasifier may be controlled to obtain synthesis gas, to be conditioned, having a suitable moisture content.
- Providing Enriched Oxygen comprises providing enriched oxygen. Enriched oxygen may be provided by any means known in the art. In embodiments, providing enriched oxygen comprises utilizing Vacuum Swing Adsorption (VSA).
- VSA Vacuum Swing Adsorption
- air is introduced via air inlet 101 into VSA apparatus 100.
- the air is introduced into one ore more adsorption vessels 108.
- the inlet air may be filtered via passage through one or more inlet filters 102.
- Air blower 103 may be used to provide the inlet air to the one or more adsorption vessels 108 via line 104.
- Enriched oxygen exits the one or more adsorption vessels 108 via line 109.
- Waste gas may be sent via vacuum blower 105 and/or discharge silencer 106 to vent line 107.
- Enriched oxygen exiting adsorption vessels 108 via line 109 may be cooled via passage through GOX cooler 110, stored as desired in buffer vessel 111, and/or compressed via GOX compressor 112 prior to introduction into synthesis gas conditioning unit 200.
- Conditioning Synthesis Gas The method further comprises subjecting the first synthesis gas to partial oxidation in the presence of at least a portion of the enriched oxygen to produce a conditioned synthesis gas having a desired ratio Of H 2 ICO in the range of from the minimum value to the maximum value. At least a portion of the enriched oxygen from VSA apparatus 100 is introduced via lines 113 and 117 into syngas conditioning unit 200.
- enriched oxygen is provided to syngas conditioning reactor 200 at a flow rate of at least 5,000 lb/h. In embodiments, enriched oxygen is provided to syngas conditioning reactor 200 at a flow rate of at least 10,000 lb/h. In embodiments, enriched oxygen is provided to syngas conditioning reactor 200 at a flow rate of at least 20,000 lb/h. In embodiments, enriched oxygen is provided to syngas conditioning reactor 200 at a flow rate in the range of from about 10,000 lb/h to about 100,000 lb/h. In embodiments, enriched oxygen is provided to syngas conditioning reactor 200 at a flow rate of at least 5 lb/h per ton of dry biomass feed.
- enriched oxygen is provided to syngas conditioning reactor 200 at a flow rate of at least 10 lb/h per ton of dry biomass feed. In embodiments, enriched oxygen is provided to syngas conditioning reactor 200 at a flow rate of at least 20 lb/h per ton of dry biomass feed. In embodiments, enriched oxygen is provided to syngas conditioning reactor 200 at a flow rate in the range of from about 10 lb/h per ton of dry biomass feed to about 100 lb/h per ton of dry biomass feed.
- Synthesis gas to be conditioned is concurrently introduced into syngas conditioning unit 200 via syngas inlet line 118.
- the enriched oxygen stream is used for partial oxidation of hydrogen with the oxygen.
- the enriched oxygen may contact the synthesis gas to be conditioned at at least one, at least 2, at least 5, or more burner(s) 112, as described hereinabove.
- the hydrogen is supplied via an upstream biomass gasifier/pyrolysis reaction.
- the upstream biomass gasifier/pyrolysis reactor produces synthesis gas with a H 2 /CO ratio which is less than 0.7 or greater than 1.5.
- the low H2/CO ratio biomass-derived syngas (BDS) reacts in a partial oxidation reaction of hydrogen gas H 2 with oxygen O 2 in a reactor to produce water and heat (H 2 and O 2 are consumed in this process).
- the amount of enriched oxygen added to the syngas conditioning reactor 200 via enriched oxygen line 113 and/or 117 is based on the desired H 2 /CO ratio in the conditioned synthesis gas exiting reactor 200 via line 201.
- the method may thus further comprise adjusting the portion (amount) of enriched oxygen based on a desired H 2 :CO ratio in the conditioned syngas.
- syngas conditioning reactor 200 comprises a reactor.
- the thermal conversion process performed in syngas conditioning reactor 200 is a non-catalytic, high temperature process.
- the high temperature is a temperature in the range of from about 950 0 C to about 1500 0 C or from about 950 0 C to about 1100 0 C.
- the amount of water in the synthesis gas to be conditioned may be controlled, as too much water in the syngas may not allow the process to achieve the lower H 2 /CO ratio (e.g., 0.75 to 1.4) range needed for certain FT processes.
- Controlling the water upstream and carefully controlling the addition of enriched oxygen to consume/react with some of the hydrogen in the synthesis gas produces heat and water. This will allow for the steam methane reaction to occur, consuming some methane and water to produce CO and H 2 , and producing synthesis gas having a desired H 2 /CO ratio.
- the synthesis gas to be conditioned (i.e., the first synthesis gas) comprises H 2 O, and the method further comprises removing at least a portion of the H 2 O from the first synthesis gas prior to partial oxidation.
- the moisture content of the synthesis gas to be conditioned is controlled by adjusting the moisture content of a carbonaceous feedstock from which the synthesis gas to be conditioned is derived (e.g. via gasification of the carbonaceous feedstock).
- the thermal conversion process in syngas conditioning reactor 200 provides the heat and steam required for steam methane reforming of the methane and other higher hydrocarbons in the supplied BDS to form H 2 and CO to the degree that it optimizes the carbon efficiency of the biomass feedstock for production of Fisher-Tropsch liquids (e.g., providing a ratio of H 2 and CO in the range of from about 0.75 to about 2.0).
- the conditioned synthesis gas is suitable for FT liquids production, in embodiments of the disclosed method.
- the conditioned synthesis gas has a ratio of H 2 /CO in the range of from about 0.75 to about 1.1, suitable, for example, for a downstream FT process.
- the conditioned synthesis gas may have a ratio of H 2 /CO in the range of from about 1.5 to about 2.0 H 2 /CO ratio, and may be suitable, for example, for use with microchannel reactors.
- the synthesis gas to be conditioned has an H 2 /CO ratio in the range of from about 0.3 to 1 on a dry basis, and the conditioned synthesis gas has a an H 2 /CO ratio in the range of from about 0.75 to about 2.
- enriched oxygen from a VSA unit is introduced into syngas conditioning reactor 200 with a biomass-derived synthesis gas having an H 2 /CO ratio in the range of from about 0.3 to about 1 on a dry basis.
- Adding enriched oxygen from a VSA unit and conditioning can yield a conditioned synthesis gas with a H 2 /CO ratio of between 0.75 and 2.
- the product conditioned syngas has a concentration of less than about 20%, 15%, 13%, or 10% inerts (including CO 2 ).
- the conditioned synthesis gas comprises less than about 50%, 40%, 30%, 20%, 10% or 5 weight percent of the tar in the synthesis gas to be conditioned.
- the conditioned synthesis gas comprises less than about 10% of the tar content of the synthesis gas to be conditioned.
- conditioning provides at least 70%, 80%, 85%, 90% or 95% reduction in tar. [0050] Cooling Conditioned Synthesis Gas.
- the method may further comprise cooling the conditioned synthesis gas. Cooling the conditioned syngas may be performed concomitantly with the production of high and/or low pressure steam.
- conditioned syngas from syngas conditioning reactor 200 is introduced via reactor outlet line 201 into HP steam boiler/superheater 202 and further into boiler 203.
- HP boiler feedwater is introduced into boiler 203 via HP BFW line 204.
- Heat exchange within boiler 203 produces heated fluid which is introduced via line 205 into HP steam boiler/superheater 202.
- Heat exchange within HP steam boiler/superheater 202 produces superheated steam, which exits HP steam boiler/superheater 202 via HP steam line 206.
- the warm synthesis gas is introduced via line 207 into LP steam boiler 209.
- Boiler feed water is introduced into LP steam boiler 209 via LP BFW line 208.
- Low pressure steam is formed by heat transfer between the warm syngas and the LP BFW, and exits LP steam boiler 209 via LP steam line 210.
- Compressing Conditioned Synthesis Gas may further comprise compressing the conditioned synthesis gas.
- the conditioned syngas which may have been cooled as described, may be introduced into synthesis gas compression apparatus 300.
- the conditioned syngas is compressed via one or more compressors 301.
- the cooled conditioned syngas exiting LP steam boiler 209 via line 211 is introduced via line 211 sequentially into four compressors 301a, 301b, 301c and 301d in the embodiment of Figure 1.
- Product water may be sent to treatment and/or disposal via product water line 302.
- the method may further comprise subjecting the conditioned syngas to further cleanup.
- one or more component may be removed from the conditioned synthesis gas.
- additional syngas cleanup is performed via one or more additional synthesis gas cleanup units 400.
- Unit(s) 400 may comprise, for example, AGR unit(s).
- Additional syngas cleanup unit is performed downstream of syngas conditioning reactor 200.
- Additional syngas cleanup may be performed downstream of one or more heat exchanger (e.g., boiler 202, 203, and/or 209), downstream of syngas compression apparatus 300, or downstream of both.
- compressed conditioned syngas is introduced via line 303 into additional cleanup unit(s) 400.
- the method may further comprise producing FT hydrocarbons from the conditioned syngas.
- Producing FT hydrocarbons may comprise introducing the conditioned syngas into one or more FT reactor(s).
- cleaned-up synthesis gas exiting additional cleanup unit(s) 400 is introduced via line 401 into FT reactor 500.
- FT reactor(s) 500 is operated under FT synthesis conditions to convert the conditioned syngas into liquid hydrocarbons.
- FT product hydrocarbons exit FT reactor(s) 500 via one or more FT product lines 501.
- Additional Features/ ⁇ dvantases Use of the disclosed system and method may increase plant yield per unit feedstock. The process may be applicable in numerous biomass- derived syngas to FT fuels projects as well as in other syngas-derived chemical processes.
- Example 1 A synthesis gas is conditioned according to the disclosed method. Parameters for the conditioning and results are presented in Tables 1 and 2 below.
- a syngas derived from biomass feedstock is fed to a conditioning reactor at a flow rate of 97,780 lb/h.
- the feedstock is 1000 TPD (dry basis).
- the feedstock comprises 11.8% moisture content.
- the flow of syngas to conditioning reactor 200 comprises 1310 lb/h hydrogen; 40,740 lb/h CO; 23,420 lb/h H 2 O; 15,448 lb/h CO 2 ; 620 lb/h nitrogen; 7,894 lb/h methane; 668 lb/h ethane; 4,606 lb/h ethylene; 46 lb/h ammonia; and 3,032 lb/h naphthalene.
- the biomass derived syngas has a temperature of 1300 0 F and a pressure of 19 psia.
- Enriched oxygen is fed to syngas conditioning reactor 200 at a flow rate of 20,892 lb/h, a temperature of 400 0 F, and a pressure of 45 psia.
- the enriched oxygen comprises 1,852 lb/h N 2 and 19,041 lb/h oxygen.
- the conditioned synthesis gas outlets reactor 200 at a flow rate of 118,672 lb/h, comprising 4,533 lb/h hydrogen; 65,694 lb/h CO; 21,234 lb/h H 2 O; 24,701 lb/h CO 2 ; 2,509 lb/h nitrogen; 0.27 lb/h methane; and 0.34 lb/h ammonia.
- the conditioned syngas has a temperature of 2100 0 F and pressure of 18 psia.
- the conditioned, compressed syngas has a flow rate of 97,688 lb/h, comprising 4,532.7 lb/h hydrogen; 65,694.1 lb/h CO; 254.8 lb/h H 2 O; 24,696.5 lb/h CO 2 ; 2,509.1 lb/h nitrogen; 0.271 lb/h methane; and 0.26 lb/h ammonia.
- the conditioned compressed synthesis gas has a temperature of 100 0 F and a pressure of 455 psia.
- Utility loads are: 2.7 MW for VSA unit, 750 lb/h of 400# saturated steam (for GOX preheater), 9.4 MW for syngas compressor, and 5,400 gpm for cooling water circulation.
- Steam generation comprises 70,500 lb/h 1000# SH (superheated) steam (exiting HP steam boiler/superheater 202 via line 206) and 11,100 lb/h 75# saturated steam (exiting LP steam boiler 209 via line 210).
- the product conditioned synthesis gas has a H 2 /CO ratio of 0.96.
- the product syngas has a concentration of 10.7% CO 2 (dry basis).
- the product conditioned syngas has a concentration of 12.6% total inerts (including CO 2 ).
- VSA Unit MW 2.7
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP10762299.5A EP2417226A4 (en) | 2009-04-06 | 2010-04-06 | SYSTEM AND METHOD FOR CONDITIONING SYNTHESIS GAS DERIVED FROM BIOMASS |
CA2758031A CA2758031A1 (en) | 2009-04-06 | 2010-04-06 | System and method for conditioning biomass-derived synthesis gas |
BRPI1011619A BRPI1011619A2 (pt) | 2009-04-06 | 2010-04-06 | processo de conversão térmica, método para produzir líquidos de produto de ft, e, sistema para condicionar gás de síntese. |
ZA2011/07092A ZA201107092B (en) | 2009-04-06 | 2011-09-28 | System and method for conditioning biomass-derived synthesis gas |
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US16685109P | 2009-04-06 | 2009-04-06 | |
US61/166,851 | 2009-04-06 |
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WO2010118022A2 true WO2010118022A2 (en) | 2010-10-14 |
WO2010118022A3 WO2010118022A3 (en) | 2011-01-20 |
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PCT/US2010/030090 WO2010118022A2 (en) | 2009-04-06 | 2010-04-06 | System and method for conditioning biomass-derived synthesis gas |
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US (1) | US20100256246A1 (pt) |
EP (1) | EP2417226A4 (pt) |
BR (1) | BRPI1011619A2 (pt) |
CA (1) | CA2758031A1 (pt) |
WO (1) | WO2010118022A2 (pt) |
ZA (1) | ZA201107092B (pt) |
Cited By (1)
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CN103339058A (zh) * | 2010-12-09 | 2013-10-02 | 普莱克斯技术有限公司 | 蒸汽甲烷转化工艺方法 |
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US8585789B2 (en) | 2010-04-13 | 2013-11-19 | Ineos Usa Llc | Methods for gasification of carbonaceous materials |
US8580152B2 (en) | 2010-04-13 | 2013-11-12 | Ineos Usa Llc | Methods for gasification of carbonaceous materials |
US8999021B2 (en) | 2010-04-13 | 2015-04-07 | Ineos Usa Llc | Methods for gasification of carbonaceous materials |
US9321641B1 (en) | 2011-02-11 | 2016-04-26 | Emerging Fuels Technology, Inc. | Process to convert natural gas into liquid fuels and chemicals |
US9034208B1 (en) | 2011-02-11 | 2015-05-19 | Emerging Fuels Technology, Inc. | Process to convert natural gas into liquid fuels and chemicals |
US20120255301A1 (en) | 2011-04-06 | 2012-10-11 | Bell Peter S | System for generating power from a syngas fermentation process |
US8895274B2 (en) * | 2011-11-28 | 2014-11-25 | Coskata, Inc. | Processes for the conversion of biomass to oxygenated organic compound, apparatus therefor and compositions produced thereby |
EP3918032A4 (en) * | 2019-01-30 | 2022-10-05 | Greenfield Global Inc. | PROCESS FOR PRODUCTION OF A SYNTHETIC FUEL |
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GB2165551B (en) * | 1984-10-10 | 1988-08-17 | Shell Int Research | Process for the production of synthesis gas |
DE4328188C2 (de) * | 1993-08-21 | 1996-04-18 | Hoechst Ag | Verfahren zur Herstellung von Synthesegas |
WO2000058242A2 (en) * | 1999-03-30 | 2000-10-05 | Syntroleum Corporation | System and method for converting light hydrocarbons into heavier hydrocarbons with a plurality of synthesis gas subsystems |
US6524370B2 (en) * | 2000-07-28 | 2003-02-25 | The Boc Group, Inc. | Oxygen production |
NL1018543C2 (nl) * | 2001-07-13 | 2003-01-14 | Droan B V | Werkwijze voor het in meerdere stappen vergassen van afval of biomassa. |
AU2003274439A1 (en) * | 2002-10-28 | 2004-05-13 | Sasol Technology (Proprietary) Limited | Production of synthesis gas and synthesis gas derived products |
US7856829B2 (en) * | 2006-12-15 | 2010-12-28 | Praxair Technology, Inc. | Electrical power generation method |
FR2910489B1 (fr) * | 2006-12-22 | 2009-02-06 | Inst Francais Du Petrole | Procede de production d'un gaz de synthese purifie a partir de biomasse incluant une etape de purification en amont de l'oxydation partielle |
-
2010
- 2010-04-06 BR BRPI1011619A patent/BRPI1011619A2/pt not_active IP Right Cessation
- 2010-04-06 US US12/754,797 patent/US20100256246A1/en not_active Abandoned
- 2010-04-06 WO PCT/US2010/030090 patent/WO2010118022A2/en active Application Filing
- 2010-04-06 CA CA2758031A patent/CA2758031A1/en not_active Abandoned
- 2010-04-06 EP EP10762299.5A patent/EP2417226A4/en not_active Withdrawn
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CN103339058A (zh) * | 2010-12-09 | 2013-10-02 | 普莱克斯技术有限公司 | 蒸汽甲烷转化工艺方法 |
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EP2417226A2 (en) | 2012-02-15 |
CA2758031A1 (en) | 2010-10-14 |
WO2010118022A3 (en) | 2011-01-20 |
ZA201107092B (en) | 2012-11-28 |
BRPI1011619A2 (pt) | 2016-03-22 |
US20100256246A1 (en) | 2010-10-07 |
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